JP2020042121A - Electrostatic latent image development toner and method of evaluating fixability of the same - Google Patents

Abstract

To provide an electrostatic latent image development toner which offers superior low-temperature fixability, medium followability, and fixing releasability on thin paper, and to provide a method of evaluating fixability of such electrostatic latent image development toner.SOLUTION: An electrostatic latent image development toner of the present invention comprises toner particles containing a binder resin containing an amorphous vinyl resin and a crystalline resin. When a dynamic viscoelastic strain dispersion measurement is performed under conditions of temperature 130°C, frequency 1 Hz, and strain amplitude 1.0-500%, and an integrated value of stress on a stress-strain curve at a strain amplitude of 100% is defined as S130 and an inclination of a major axis is defined as θ130, S130 is greater than 0 Pa and equal to or less than 350000 Pa, and θ130 is equal to or greater than 0° and less than 10°.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic latent image and a method for evaluating the fixing property of the toner for developing an electrostatic latent image, and more particularly, to an electrostatic latent image developing method which is excellent in low-temperature fixing property, medium followability, and fixing and peeling property of thin paper. The present invention relates to a method for evaluating the fixability of a toner for developing and a toner for developing an electrostatic latent image.

In recent years, demands from the market for speeding up and energy saving of image forming apparatuses have been demanded for toners that are excellent in low-temperature fixing property and can provide high-quality images. For toners, lowering the melting temperature and melt viscosity of the binder resin is expected to achieve low-temperature fusing, and furthermore, it is expected to improve the followability of media such as uneven paper. I am concerned.
For example, in the technique disclosed in Patent Document 1, in a toner image forming method with a high-speed system, the toner contains at least an amorphous polyester resin, a crystalline polyester resin, a colorant, and a release agent, By defining the value of the central activation energy E (50), in a high-speed output system, the photoreceptor filming (contamination) property is improved, low-temperature fixing is possible, and toner preservability is good, and fixing high-temperature winding is achieved. Properties and fixing strength. Further, it is suggested that a fatty acid amide compound is contained as a crystallinity retaining component, and the fatty acid amide compound is intended to further improve low-temperature fixability due to the effect of lowering the viscosity of the crystalline polyester resin due to the amide structure. However, the ability to follow media such as uneven paper was not achieved.
In addition, for example, in the technique disclosed in Patent Document 2, a toner containing a block copolymer composed of a crystalline segment and an amorphous segment as a binder resin has a maximum elastic stress measured by a large amplitude vibration method (LAOS). By defining parameters such as values, the toner is improved in abrasion resistance, pigment dispersibility, and mechanical durability in addition to compatibility between low-temperature fixability and heat-resistant storage stability. However, in the parameter range shown in Patent Document 2, the toner shows low-temperature fixability while maintaining a certain elastic modulus, and the toner has a tendency to have a large elastic modulus. there were.

JP 2009-69222A JP-A-2005-055661

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and circumstances, and a problem to be solved is to provide a toner for developing an electrostatic latent image and an electrostatic latent image which are excellent in low-temperature fixability, medium followability, and fixability of thin paper. An object of the present invention is to provide a method for evaluating the fixing property of a developing toner.

In order to solve the above-mentioned problem, the present inventor, in the course of examining the cause of the above-mentioned problem, has a dynamic viscoelasticity of a toner containing a crystalline resin and an amorphous vinyl resin at a temperature of 130 ° C. and a strain amplitude of 100%. By defining the area and slope represented by the stress-strain curve drawn in the measurement in a specific range, the toner for developing an electrostatic latent image and the toner having excellent low-temperature fixability, medium followability, and thin paper fixability and peelability are provided. The present inventors have found that a method for evaluating fixability can be provided, and have reached the present invention.
That is, the above object according to the present invention is solved by the following means.

1. An electrostatic latent image developing toner including toner particles containing a binder resin,
The binder resin contains an amorphous vinyl resin and a crystalline resin, and performs dynamic viscoelastic strain dispersion measurement under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%. When the integrated value of the stress of the stress-strain curve at an amplitude of 100% is S130, and the inclination of the major axis is θ130,
S130 is more than 0 Pa and not more than 350000 Pa,
The toner for developing an electrostatic latent image, wherein θ130 is 0 ° or more and less than 10 °.

  2. 2. The toner for developing an electrostatic latent image according to claim 1, wherein S130 is more than 0 Pa and 100000 Pa or less.

  3. 3. The toner for developing an electrostatic latent image according to claim 1, wherein the θ130 is in a range of 0 to 8 °.

  4. 4. The electrostatic latent element according to any one of items 1 to 3, wherein the net intensity of sodium measured by X-ray fluorescence analysis is in the range of 0.1 to 0.7. Image developing toner.

  5. 5. The electrostatic device according to claim 1, wherein a content of the crystalline resin is in a range of 3 to 30% by mass based on a total amount of the binder resin. 6. Latent image developing toner.

  6. 6. The electrostatic latent image developing toner according to any one of items 1 to 5, wherein the crystalline resin contains a crystalline polyester resin.

  7. 7. The toner for developing an electrostatic latent image according to any one of claims 1 to 6, wherein the binder resin contains a fatty acid derivative in addition to the crystalline resin.

  8. When the content of the crystalline resin is a [mass%] and the content of the aliphatic derivative is b [mass%], the value b / a of b to a is in the range of 0.1 to 1. Item 8. The toner for developing an electrostatic latent image according to Item 7, wherein

  9. 9. The toner for developing an electrostatic latent image according to claim 7, wherein the fatty acid derivative is a fatty acid alkylamide compound.

  10. 10. The toner for developing an electrostatic latent image according to claim 9, wherein the fatty acid alkylamide compound has an amide bond at a molecular terminal.

  11. 11. The toner for developing an electrostatic latent image according to any one of items 7 to 10, wherein a melting point of the fatty acid derivative is in a range of 40 to 110 ° C.

  12. 12. The electrostatic latent image developing toner according to any one of items 7 to 11, wherein the fatty acid derivative has a weight average molecular weight in a range of 200 to 550.

13. The dynamic viscoelastic strain dispersion measurement is performed under the following various conditions A, and when the inclination of the major axis of the stress-strain curve at a strain amplitude of 100% under the following condition A (3) is θ70, the θ70 is 10 to 48 °. Item 13. The toner for developing an electrostatic latent image according to any one of Items 1 to 12, wherein
<< Condition A >>
(1) Temperature: 130 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(2) Temperature: 100 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(3) Temperature: 70 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 100%
Measure in order.

14． A method for evaluating the fixability of a toner for developing an electrostatic latent image, comprising:
A dynamic viscoelastic strain dispersion measurement is performed under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%, and an integrated value of a stress and a slope of a major axis of a stress-strain curve at a strain amplitude of 100% are calculated. A method for evaluating the fixability of the toner for developing an electrostatic latent image.

By the means of the present invention, it is possible to provide a toner for developing an electrostatic latent image and a method for evaluating the fixability of the toner for developing an electrostatic latent image, which are excellent in low-temperature fixing property, medium followability, and thin paper fixing and peeling property. .
Although the mechanism of expression or action of the effect of the present invention has not been clarified, it is speculated as follows.
Conventionally, as the melting deformation of the toner, the effect on the fixing property has been predicted from the softening point obtained by measuring the change in the melting state of the toner while applying a constant weight to the toner being heated. However, when examining the relationship between the actual softening point and the fixability, it often turns out that the information is inconsistent, and it has been found that information from the softening point alone is not enough to predict the fixability. Therefore, in the present invention, the melting deformation of the toner in the fixing process in which the temperature, the linear velocity, and the pressure are applied to the toner is considered from the viewpoint of rheology.

When a periodically changing strain is applied to a viscoelastic body such as a toner, a phase difference occurs between the generated stress and a stress-strain curve (Lissajous) area defined by the change in the stress and the strain. It is known that this corresponds to heat generation, that is, energy lost due to deformation (Reference: Japanese Patent Application Laid-Open No. 11-237332).
FIG. 1 shows the stress and strain characteristics of a viscoelastic body with time on the horizontal axis, and FIG. 2 shows the stress and strain characteristics with strain on the horizontal axis and stress on the vertical axis (stress-strain curve). .
As shown in FIG. 1, in a viscoelastic body, the phase of stress is delayed by δ with respect to strain, where 0 <δ <π / 2. Further, as shown in FIG. 2, the stress-strain curve of the viscoelastic body is elliptical, and the area S of the ellipse is energy lost during one cycle of deformation, and corresponds to heat generation energy.
Therefore, in the toner in the fixing process, the energy required for the melt deformation corresponding to the area of the stress-strain curve is an index of the low-temperature fixability.
If the area of the stress-strain curve is small, the energy required for deformation is small, so the low-temperature fixability (minimum fixing temperature) is excellent. On the other hand, if the area is large, the energy required for deformation is large, so the low-temperature fixability is low. Is presumed to be disadvantageous.
Further, since the elastic modulus can be obtained by dividing the stress by the strain (stress ÷ strain = elastic modulus), the slope of the ellipse of the stress-strain curve indicates the angle between the major axis of the ellipse and the horizontal axis shown in FIG. And the elastic modulus of the toner obtained from the strain applied at the measurement temperature. The ductility of the toner can be understood from the magnitude of the elastic modulus. If the elastic modulus is small (the inclination is small), the toner is likely to expand due to deformation and hard to return to its original state, so it is presumed that the toner has excellent followability to media such as paper and easily penetrates into uneven paper or paper fibers.
On the other hand, if the elastic modulus is large (the inclination is large), even if energy due to deformation is applied to the toner, a force to extend it once but to return to the original state is exerted (toner elasticity recovery).
Therefore, the range defined in the present invention, that is, the range where S130 is more than 0 Pa and less than or equal to 350000 Pa, and the range where θ130 is 0 ° or more and less than 10 ° is easy to be deformed with small energy, and the elastic modulus is small = elastic recovery. Since it has the characteristics that it is difficult to recover and it does not return to its original state, excellent low-temperature fixability and medium followability (easy to bite into paper irregularities) are ensured.
In the present invention, low-temperature fixability (minimum fixation temperature) and media followability are achieved by regarding the conditions of 130 ° C. and 100% strain as actual fixing conditions, and optimizing the area of the stress-strain curve and the range of its slope. We were able to.
That is, the area obtained by the dynamic viscoelasticity measurement under the conditions of 130 ° C. and 100% strain is a range in which the low-temperature fixability is achieved. If the area is larger than the designated area, the energy required for the deformation is too large, so that the low-temperature fixability is difficult. If the inclination is larger than the specified inclination, the elasticity is too large, so that the fused toner is difficult to deform, or the force to return to the original state even if it deforms acts, and it is estimated that the followability to paper will be disadvantageous. Is done.

Graph showing changes in stress and strain when time is represented on the horizontal axis for general viscoelastic materials A graph (stress-strain curve) obtained by converting strain into abscissa and stress into ordinate in the graph of FIG. Schematic diagram showing the slope of the major axis of the stress-strain curve Schematic diagram showing strain application in strain dispersion measurement of dynamic viscoelasticity For the toner 1 in the example, a dynamic viscoelastic strain dispersion measurement was performed under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%, and a change in stress when a strain was applied at a strain amplitude of 100%. The resulting stress-strain curve

The toner for developing an electrostatic latent image of the present invention is a toner for developing an electrostatic latent image containing toner particles containing a binder resin, wherein the binder resin contains an amorphous vinyl resin and a crystalline resin. Then, a dynamic viscoelastic strain dispersion measurement was performed under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%, and the integrated value of the stress of the stress-strain curve at a strain amplitude of 100% was S130. When the inclination is θ130, S130 is more than 0 Pa and 350000 Pa or less, and θ130 is 0 ° or more and less than 10 °.
This feature is a technical feature common or corresponding to each of the following embodiments.

As an embodiment of the present invention, it is preferable that S130 is more than 0 Pa and not more than 100,000 Pa in terms of designing a polymer for a toner, and is also preferable in that it is excellent in low-temperature fixability and media followability.
In addition, it is preferable that the above-mentioned θ130 is in the range of 0 to 8 ° from the viewpoint of excellent media followability.

  When the net intensity of sodium measured by X-ray fluorescence analysis is in the range of 0.1 to 0.7, the amount of the interaction formed between sodium in the toner and the main resin may be too large. The amount is not too small, and the amount of the release agent oozes out.

It is preferable that the content of the crystalline resin is in the range of 3 to 30% by mass based on the total amount of the binder resin. When the content is 3% by mass or more, the compatibility between the crystalline polyester resin and the amorphous vinyl resin in the image after fixing is suppressed, and when the content is 30% by mass or less, the crystalline polyester resin in the image after fixing is And an amorphous resin in an amount suitable for suppressing the phase separation state.
It is preferable that the crystalline resin contains a crystalline polyester resin from the viewpoint of improving low-temperature fixability.
Further, the binder resin preferably contains a fatty acid derivative in addition to the crystalline resin, and in particular, the fatty acid derivative may be a fatty acid alkylamide compound, and the crystallinity of the crystalline polyester resin by the fatty acid alkylamide compound Is advantageous in that the low-temperature fixability can be improved and the fixing offset and the fixing wrap can be prevented by the holding effect of the above.

  When the content of the crystalline resin is a [mass%] and the content of the aliphatic derivative is b [mass%], the value b / a of b to a is in the range of 0.1 to 1. Is preferred in that the plasticizing effect of the fatty acid derivative can be brought out, the low-temperature fixability can be improved, and the fixability and releasability of thin paper can be improved.

  It is preferable that the fatty acid alkylamide compound has an amide bond at a molecular terminal, since a strong interaction with the main resin is developed and a plasticizing effect of the main resin is promoted.

  When the melting point of the fatty acid derivative is in the range of 40 to 110 ° C., and the weight average molecular weight of the fatty acid derivative is in the range of 200 to 550, the fixing peeling caused by the offset accompanying the lowering of the viscosity. This is preferable because the fixability does not decrease, and a plastic effect (melting) can be achieved with respect to the applied heat of the main resin, and the effect of improving the fixability can be exhibited.

  The dynamic viscoelastic strain dispersion measurement is performed under the various conditions A, and when the slope of the major axis of the stress-strain curve at a strain amplitude of 100% under the condition A (3) is defined as θ70, the θ70 is 10 to 48 °. It is preferable that the ratio be within the range described above, since the fixing and releasability of the thin paper is improved and a high gloss image is obtained.

  The method for evaluating the fixability of the toner for developing an electrostatic latent image according to the present invention measures the dynamic viscoelastic strain dispersion under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%. It is characterized in that the integrated value of the stress of the stress-strain curve at 100% and the inclination of the major axis are calculated. As a result, it is possible to more accurately predict the fixing property as compared with the conventional case where the fixing property is predicted from the information from the softening point.

  Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described. In addition, in this application, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit.

[Electrostatic latent image developing toner]
The electrostatic latent image developing toner of the present invention (hereinafter, also simply referred to as toner) is an electrostatic latent image developing toner containing a binder resin, wherein the binder resin is an amorphous vinyl resin and A dynamic viscoelastic strain dispersion measurement is performed under the conditions of a crystalline resin, a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%. Is S130 and the inclination of the major axis is θ130, the S130 is more than 0 Pa and 350000 Pa or less, and the θ130 is 0 ° or more and less than 10 °.

<Method of calculating S130 and θ130>
(Dynamic viscoelastic strain dispersion measurement)
The distortion dispersion measurement of the dynamic viscoelasticity of the toner is performed using ARES-G2 manufactured by TA Instruments.
First, a pressure of 20 MPa is applied to 0.2 g of the toner powder by a compression molding machine for 30 seconds to produce pellets having a thickness of 2.0 mm ± 0.3 mm and 1 cmφ. Next, the upper side of the pellet was set on an aluminum disposable parallel plate of 8 mmφ, and the lower side was set on an aluminum disposable parallel plate of 25 mmφ. After the temperature was raised to 130 ° C., the pellet was compressed to a predetermined gap and protruded into the upper parallel plate. Trim the melt.
The sample is set so that the initial normal force becomes zero. Then, in the subsequent measurement, the effect of the normal force is canceled by setting the automatic tension adjustment (Auto Tension Adjustment ON). The measurement conditions are set as follows, and as shown in FIG. 4, three cycles of strain are applied for each strain amplitude, and the stress at that time is measured.
1. 1. Use a parallel plate with a diameter of 8 mm. 2. Set the measurement gap to 1 mm. 3. Set the frequency (Frequency) to 1 Hz. The applied strain amplitude (Strain) is 1.0% (Initial), 1.5%, 2.5%, 4%, 6%, 10%, 16%, 25%, 40%, 62%, 100%, Set to 158%, 250%, 400%, 500% (Final).

(Stress-strain curve analysis)
In the above-described dynamic viscoelastic strain dispersion measurement, stress data when a strain is applied for one cycle with a strain amplitude of 100% is collected, and the horizontal axis represents the strain γ, and the vertical axis represents the stress σ. A stress-strain curve is created such that the scale for 100% of the strain γ is equal to the scale for 1500 Pa of the stress σ. A stress-strain curve is similarly created for the remaining two cycles at a strain amplitude of 100%, and a stress-strain curve for a total of three cycles is obtained.
For each curve, the integrated value [Pa] of stress σ is calculated by TRIOS (manufactured by TA Instruments Co., Ltd.), and the integrated value of stress σ for three cycles of the curve is averaged to calculate S130 [Pa].
As shown in FIG. 3, a point A (a, b) having the longest distance from the center point (0, 0) of the stress-strain curve is specified, and the point A and the center point are connected by a straight line. Is assumed to be B at the point where the stress-strain curve intersects, and a straight line connecting point A and point B (passing through the center point) is defined as the major axis. The minor axis refers to a straight line that connects two points where a straight line that intersects the major axis at right angles and a stress-strain curve intersect. The inclination θ refers to the angle between the major axis and the horizontal axis, and can be calculated by obtaining tan θ = | b | / | a | from the coordinate value of the end point A (a, b) forming the major axis. Θ for three cycles of the curve is averaged to obtain θ130 [°].

If the area of the stress-strain curve is small, the energy required for deformation is small, so the low-temperature fixability (minimum fixing temperature) is excellent. On the other hand, if the area is large, the energy required for deformation is large, so the low-temperature fixability is low. It is presumed that it will be disadvantageous for media followability.
As a requirement for low-temperature fixability, it is important that the area is small. However, when the area is zero, the stress-strain curve shows a straight line and represents a pure elastic body (rubber). Must be greater than zero. On the other hand, if the area is too large, the energy required for deformation increases, and it is difficult to achieve low-temperature fixability and medium followability.
Therefore, the toner of the present invention is characterized in that the S130 is more than 0 Pa and 350000 Pa or less, preferably, the S130 is more than 0 Pa and 100000 Pa or less, and particularly preferably more than 0 Pa and 80000 Pa or less.

Also, the modulus of elasticity can be obtained by dividing the stress by the strain (stress / strain = elastic modulus). That is, the slope of the major axis of the stress-strain curve indicates the elastic modulus. The ductility of the toner can be understood from the magnitude of the elastic modulus.
If the inclination θ130 of the major axis is less than 10 °, the toner is liable to be extended by deformation, so it is presumed that the toner has excellent followability to a medium such as paper and easily penetrates into uneven paper or fiber of paper. It is preferable that the inclination θ130 of the major axis be in the range of 0 to 8 °.

S130 and θ130 within the above ranges can be achieved by satisfying all of the following (i) to (iii).
(I) Combination of Crystalline Resin and Fatty Acid Derivative The fatty acid derivative described below, particularly the fatty acid amide compound, has high polarity, so that it is likely to cause intermolecular interaction with the polar group of the crystalline resin or the main resin, thereby reducing the temperature at low temperatures. Can be reduced in viscosity.
(Ii) Simultaneous emulsification of the crystalline resin and the fatty acid derivative The interaction between the crystalline resin and the fatty acid derivative is improved, and a synergistic effect can be brought about in reducing the viscosity of the main binder.
In addition, when the dispersion of the crystalline resin and the fatty acid derivative are separately introduced in the association (particulation) step, the interaction decreases and the system becomes unstable, but the simultaneous emulsification of the crystalline resin and the fatty acid derivative causes It is considered that by maintaining the crystalline resin and the fatty acid derivative in the same dispersion liquid stably, the toner particles can be expressed without deteriorating their functions.
(Iii) Divided addition of dispersion liquid of crystalline resin and fatty acid derivative (initial addition and completion of heating)
By separately adding the dispersion liquid of the crystalline resin and the fatty acid derivative at the initial stage (before the temperature rise) and after the completion of the temperature rise, the toner can be uniformly dispersed throughout the toner. Thereby, the effect of lowering the viscosity of the main binder is further exhibited. With only the initial addition, the crystalline resin and the fatty acid derivative are arranged only inside, and after the temperature rise is completed, the crystalline resin and the fatty acid derivative are arranged only outside the toner. In order to effectively lower the viscosity of the main binder, it is necessary to uniformly disperse the toner throughout the toner.

[Θ70]
The toner of the present invention is subjected to dynamic viscoelastic strain dispersion measurement under the following various conditions A, and when the slope of the major axis of the stress-strain curve at a strain amplitude of 100% under the following condition A (3) is θ70, It is preferable that θ70 is in the range of 10 to 48 °.
<< Condition A >>
(1) Temperature: 130 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(2) Temperature: 100 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(3) Temperature: 70 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 100%
Measure in order.

<Method for calculating θ70>
The dynamic viscoelastic strain dispersion measurement is performed under the following condition A in the same manner as in the section (Measurement of Dynamic Viscoelastic Strain Dispersion) in <Calculation Method of S130 and θ130>. In the following condition A, “strain amplitude: 1.0 to 500%” means that the applied strain amplitude is 1.0% (Initial), 1.5%, 2.5%, 4%, 6%, 10%. %, 16%, 25%, 40%, 62%, 100%, 158%, 250%, 400%, 500% (Final). As shown in FIG. 4, three cycles of strain are applied for each strain amplitude, and the stress at that time is measured.
<< Condition A >>
(1) Temperature: 130 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(2) Temperature: 100 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(3) Temperature: 70 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 100%
In the dynamic viscoelastic strain dispersion measurement under the condition A (3), data of stress when strain is applied for three cycles at a strain amplitude of 100% is collected, and the strain γ is plotted on the horizontal axis for each cycle. The stress σ is plotted on the vertical axis. At this time, a stress-strain curve is created so that the scale of 100% of the strain γ is equal to the scale of 250,000 Pa of the stress σ. obtain. In this regard, θ70 [°] is calculated in the same manner as in (Stress and Strain Curve Analysis) in <S130 and θ130 Calculation Method>.

70 ° C. is a temperature assumed immediately after fixing the toner. From the temperature 70 ° C. and the inclination θ70 of the stress-strain curve of 100% strain, the molecular mobility of the toner and the resin elastic recovery force at the temperature assumed immediately after fixing are obtained. I understand.
When the inclination (elastic modulus) θ70 is 10 ° or more, the mobility of the melted toner is small, so that the elastic recovery force is large, and the fixing releasability, particularly the fixing releasability of thin paper, is excellent. When the angle is equal to or less than 48 °, the elastic recovery force is small, so that a high gloss image can be obtained without deteriorating the smoothness of the image surface.
The angle θ70 is preferably larger than 12 ° and equal to or smaller than 45 °.

  In order to make the above-mentioned θ70 within the above range, the amount of the crystalline resin is larger than 1% by mass and the melting point of the fatty acid derivative is 110 ° C. or less, which can be achieved.

<Sodium Net Strength>
The toner of the present invention preferably has a Net intensity of sodium measured by X-ray fluorescence analysis in the range of 0.1 to 0.7.
As described above, when the effect of lowering the viscosity is exerted, poor peeling (fixing / separability) from thin paper deteriorates. In this case, it is presumed that the cause is that the elasticity of the toner itself does not exert an effect on the separation from the fixing belt. Therefore, the interaction between sodium (Na) contained in the toner and the main resin (interaction between Na and a functional group that interacts with Na of the binder resin, for example, a carboxy group, a sulfonium group, etc.) By adjusting the amount of formation, the amount of the release agent (wax) exuded can be controlled.
If the amount of interaction between Na in the toner and the binder resin is too large, the release agent is less likely to exude, and if the amount is too small, the release agent is more likely to exude on the toner surface. Since the amount of generated dust increases, the Net strength is preferably in the range of 0.1 to 0.7, more preferably in the range of 0.15 to 0.65, and 0.1 to 0.65. It is particularly preferred that it is in the range of 2 to 0.65.

(Method of measuring the net strength of sodium)
As a pre-measurement process, 1 g of the toner is compression-molded by a pressure molding machine under a pressure of 15 tons for 10 seconds. Then, the compression molded sample was subjected to a total elemental analysis using a fluorescent X-ray apparatus XRF-1700 manufactured by Shimadzu Corporation under the measurement conditions of a tube voltage of 40 KV and a tube current of 95 mA to measure the Net intensity of sodium. Do.

<Toner base particles>
The toner of the present invention includes toner particles containing a binder resin.
In the present invention, toner particles refer to toner base particles to which an external additive is added, and an aggregate of toner particles is referred to as toner. In general, the toner base particles can be used as they are as they are, but in the present invention, toner base particles obtained by adding an external additive to the toner base particles are used.

  The toner base particles according to the present invention contain a binder resin. Further, the toner base particles according to the present invention may contain other components such as a release agent (wax), a colorant, and a charge control agent, if necessary.

<Binder resin>
The binder resin according to the present invention contains an amorphous vinyl resin and a crystalline resin.

<Amorphous vinyl resin>
An amorphous vinyl resin is a resin obtained by polymerization using at least a vinyl monomer.
For example, acrylic resin, styrene / acrylic copolymer resin, ethylene / vinyl acetate resin and the like can be mentioned. The amorphous vinyl resin is easy to control the phase separation from the crystalline resin. Above all, in consideration of the productivity in the emulsion aggregation method (that is, a toner having a sharp particle size distribution can be obtained by producing a latex having a uniform aggregation property) and the plasticity at the time of heat fixing, styrene and acrylic Polymer resins are preferred. The amorphous vinyl resin may be used alone or in combination of two or more.

The lower limit of the content of the amorphous vinyl resin is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or more based on the total amount of the binder resin. Even more preferably, it is particularly preferably 60% by mass or more. When the content is 5% by mass or more, the compatibility with the crystallized resin is good, and the low-temperature fixability is good.
Further, from the viewpoint of improving the low-temperature fixability, the upper limit of the content of the amorphous vinyl resin is preferably 99% by mass or less, and more preferably 95% by mass or less.
The content of the amorphous vinyl resin is the content of all the amorphous vinyl resins with respect to the total amount of the binder resin. Therefore, for example, when the binder resin includes, in addition to the amorphous vinyl resin and the crystalline resin, a hybrid resin having a hybrid structure with the amorphous vinyl resin, as a main component contained in the toner, In addition to the content of the amorphous vinyl resin, the content of the amorphous vinyl polymer segment in the hybrid resin is also included in the content of the amorphous vinyl resin.

(1) Styrene monomer Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert- Butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof.

(2) (Meth) acrylic acid ester monomer Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ( T-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, (meth) Diethylaminoethyl acrylate, dimethylaminoethyl (meth) acrylate and derivatives thereof.

(3) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate and the like.

(4) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether and the like.

(5) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone and the like.

(6) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like.

(7) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Further, as the vinyl monomer, it is preferable to use a monomer having an ionic dissociation group such as a carboxy group, a sulfonic group, and a phosphate group. Specifically, there are the following.
Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl maleate and monoalkyl itaconate.
Examples of the monomer having a sulfonic acid group include styrenesulfonic acid, allylsulfosuccinic acid, and 2-acrylamido-2-methylpropanesulfonic acid.
Furthermore, examples of the monomer having a phosphate group include acid phosphooxyethyl methacrylate.

  Further, a polyfunctional vinyl may be used as the vinyl monomer, and the amorphous vinyl resin may have a crosslinked structure. Polyfunctional vinyls include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, and neopentyl glycol. Diacrylate and the like.

The method for producing the amorphous vinyl resin is not particularly limited, and a peroxide, a persulfide, a persulfate, an arbitrary polymerization initiator such as an azo compound, which is generally used for the polymerization of the above monomers, may be used as a bulk. A method of performing polymerization by a known polymerization method such as a polymerization method, a solution polymerization method, an emulsion polymerization method, a miniemulsion method, and a dispersion polymerization method is exemplified.
The amorphous vinyl resin is preferably an amorphous resin having a glass transition temperature (Tg) in a range of 25 to 60 ° C, and a non-crystalline resin having a glass transition temperature (Tg) in a range of 35 to 55 ° C. More preferably, it is a crystalline resin.

  In addition, in this specification, the glass transition temperature (Tg) of a resin is a value measured using "Diamond DSC" (manufactured by PerkinElmer Japan Co., Ltd.). As a measurement procedure, 3.0 mg of a measurement sample (resin) is sealed in an aluminum pan and set in a holder. An empty aluminum pan was used as a reference. The measurement was performed at a measurement temperature of 0 to 200 ° C., a heating rate of 10 ° C./min, and a cooling rate of 10 ° C./min. Analysis was performed based on the data in Heat, and an extension line of the baseline before the rising of the first endothermic peak and a tangent line showing the maximum slope from the rising portion of the first peak to the peak apex were drawn. The intersection is defined as the glass transition temperature.

  The molecular weight of the amorphous vinyl resin measured by gel permeation chromatography (GPC) is preferably in the range of 10,000 to 100,000 in terms of weight average molecular weight (Mw).

In this specification, the molecular weight of the resin by GPC is a value measured as follows.
That is, using an apparatus “HLC-8120GPC” (manufactured by Tosoh Corporation) and columns TSKgel guardcolumn SuperHZ-L and “TSKgel SuperHZM-M” (manufactured by Tosoh Corporation), the carrier solvent was maintained at a column temperature of 40 ° C. And flowing tetrahydrofuran (THF) at a flow rate of 0.2 mL / min, and dissolving the measurement sample (resin) in tetrahydrofuran so as to have a concentration of 1 mg / ml under a dissolution condition of performing treatment using an ultrasonic disperser at room temperature for 5 minutes. .
Next, a sample solution was obtained by treating with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution was injected into the apparatus together with the above-mentioned carrier solvent, and detected using a refractive index detector (RI detector) to perform measurement. The molecular weight distribution of the sample is calculated using a calibration curve measured using monodisperse polystyrene standard particles. Ten points are used as polystyrene for the calibration curve measurement.

<Crystalline resin>
The content of the crystalline resin according to the present invention is preferably in the range of 3 to 30% by mass based on the total amount of the binder resin. More preferably, it is in the range of 5 to 20% by mass, and particularly preferably in the range of 15 to 20% by mass.
When the content ratio of the crystalline resin in the binder resin is 3% by mass or more, the compatibility between the crystalline resin and the amorphous vinyl resin in the image after fixing is suppressed, and the content is 30% by mass or less. The amount is an appropriate amount for suppressing the phase separation between the crystalline resin and the amorphous vinyl resin in the image after fixing.

<Crystalline polyester resin>
It is preferable that the crystalline resin contains a crystalline polyester resin.
The crystalline polyester resin is a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyhydric carboxylic acid component) and / or a hydroxycarboxylic acid and a divalent or higher valent alcohol (polyhydric alcohol component). Among them, a resin having a distinct melting peak instead of a stepwise endothermic change in differential scanning calorimetry (DSC). The clear melting peak is, specifically, in the DSC curve obtained by the differential scanning calorimetry of the crystalline polyester resin alone, the half width of the melting peak in the second heating process is within 15 ° C. It means a peak.

  The melting point of the crystalline polyester resin is preferably in the range of 65 to 85 ° C, more preferably in the range of 75 to 85 ° C. When the melting point of the crystalline polyester resin is in the above range, sufficient low-temperature fixability and excellent image storability can be obtained. The melting point of the crystalline polyester resin can be controlled by the resin composition. Here, the melting point of the crystalline polyester resin is the peak top temperature of the melting peak in the second heating process in the DSC curve obtained by the differential scanning calorimetry of the crystalline polyester resin alone. When a plurality of melting peaks exist in the DSC curve, the peak top temperature of the melting peak having the largest endothermic amount is defined as the melting point.

  The melting point (Tm) of the crystalline polyester resin is the peak temperature of the endothermic peak and can be measured by DSC using diamond DSC (manufactured by PerkinElmer). Specifically, a sample was prepared using an aluminum pan KITNo. B0143013, set in a sample holder of a thermal analyzer Diamond DSC (manufactured by PerkinElmer), and change the temperature in the order of heating, cooling and heating. During the first heating, the temperature is raised from room temperature (25 ° C.) to 0 ° C. during the second heating, to 150 ° C. at a heating rate of 10 ° C./min, and kept at 150 ° C. for 5 minutes. The temperature is decreased from 150 ° C. to 0 ° C. at a temperature decreasing rate of 0 ° C./min, and the temperature of 0 ° C. is maintained for 5 minutes. The temperature at the peak top of the endothermic peak in the endothermic curve obtained at the time of the second heating is measured as the melting point.

  The polyvalent carboxylic acid component for forming the crystalline polyester resin is a compound containing two or more carboxy groups in one molecule. Specifically, for example, saturated aliphatic dicarboxylic acids such as succinic acid, sebacic acid and dodecane diacid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Trivalent or more polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides of these carboxylic acid compounds or alkyl esters having 1 to 3 carbon atoms. It is preferable to use a saturated aliphatic dicarboxylic acid as a polyvalent carboxylic acid component for forming a crystalline polyester resin. These may be used alone or in combination of two or more.

  The polyhydric alcohol component for forming the crystalline polyester resin is a compound containing two or more hydroxy groups in one molecule. Specifically, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Aliphatic diols such as heptanediol, 1,8-octanediol, neopentylglycol, and 1,4-butenediol; trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol; . As the polyhydric alcohol component for forming the crystalline polyester resin, it is preferable to use an aliphatic diol. These may be used alone or in combination of two or more.

  The method for producing the crystalline polyester resin is not particularly limited, and it can be produced using a general polyester polymerization method in which the above-mentioned polycarboxylic acid and polyhydric alcohol are reacted under a catalyst, for example, directly. It is preferable to use a polycondensation or transesterification method depending on the type of the monomer.

Further, a linear aliphatic hydroxycarboxylic acid can be used in combination with the above-mentioned polyhydric carboxylic acid and / or polyhydric alcohol. Examples of the linear aliphatic hydroxycarboxylic acid for forming the crystalline polyester resin include 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxypentanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, -Hydroxydecanoic acid, 12-hydroxydodecanoic acid, 14-hydroxytetradecanoic acid, 16-hydroxyhexadecanoic acid, 18-hydroxyoctadecanoic acid: and lactone compounds in which these hydroxycarboxylic acids are cyclized, or alcohols having 1 to 3 carbon atoms And alkyl esters thereof. These may be used alone or in combination of two or more.
In addition, when a crystalline polyester resin is formed, it is preferable to use a polyvalent carboxylic acid and a polyhydric alcohol component, since the reaction can be easily controlled and a resin having a desired molecular weight can be obtained.

Examples of the catalyst that can be used for the production of the crystalline polyester resin include titanium catalysts such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and dibutyltin dichloride, dibutyltin oxide, and diphenyltin oxide. And the like.
The usage ratio of the above-mentioned polyhydric carboxylic acid component and polyhydric alcohol component is such that the equivalent ratio [OH] / [COOH] of the hydroxy group [OH] of the polyhydric alcohol component and the carboxy group [COOH] of the polyhydric carboxylic acid component. ] Is preferably in the range of 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.

  The crystalline polyester resin preferably has an acid value in the range of 5 to 30 mgKOH / g, more preferably 10 to 25 mgKOH / g, and still more preferably 15 to 25 mgKOH / g. This acid value represents the mass of potassium hydroxide (KOH) required for neutralizing the acid contained in 1 g of the sample in mg unit. The acid value of the resin is measured by the following procedure according to JIS K0070-1992.

(Preparation of reagents)
Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and prepare a phenolphthalein solution. 7 g of JIS special grade potassium hydroxide is dissolved in 5 mL of ion-exchanged water, and ethyl alcohol (95% by volume) is added to make 1 liter. After leaving the container in an alkali-resistant container for 3 days so as not to be exposed to carbon dioxide, the mixture is filtered to prepare a potassium hydroxide solution. Orientation follows the description of JIS K0070-1992.

(main exam)
2.0 g of the pulverized sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (toluene: ethanol at a volume ratio of 2: 1) is added, and the mixture is dissolved for 5 hours. Next, several drops of a phenolphthalein solution prepared as an indicator are added, and titration is performed using the prepared potassium hydroxide solution. The end point of the titration is the time when the light red color of the indicator continues for about 30 seconds.

(Blank test)
Except that no sample is used (that is, only a mixed solution of toluene / ethanol (toluene: ethanol at a volume ratio of 2: 1) is used), the same operation as in the above-described test is performed.
The acid value is calculated by substituting the titration results of this test and blank test into the following equation (1).
Formula (1) A = [(CB) × f × 5.6] / S
A: Acid value (mgKOH / g)
B: Amount of potassium hydroxide solution added during blank test (mL)
C: Addition amount of potassium hydroxide solution at the time of this test (mL)
f: Factor of 0.1 mol / L potassium hydroxide ethanol solution S: Mass of sample (g)

  The molecular weight of the crystalline polyester resin is such that the weight average molecular weight (Mw) calculated from the molecular weight distribution measured by gel permeation chromatography (GPC) is in the range of 5000 to 50,000, and the number average molecular weight (Mn) is 1500 to 25000. Is preferably within the range.

The molecular weight measurement by GPC is performed as follows.
That is, using an apparatus “HLC-8320” (manufactured by Tosoh Corporation) and columns “TSKgel guardcolumn SuperHZ-L” and “TSKgel SuperHZM-M” (manufactured by Tosoh Corporation), the column temperature was kept at 40 ° C., and the carrier solvent was used. Flow tetrahydrofuran (THF) at a flow rate of 0.2 ml / min. The measurement sample (crystalline polyester resin) is dissolved in tetrahydrofuran so as to have a concentration of 1 mg / ml under a dissolution condition in which the sample is treated at room temperature for 5 minutes using an ultrasonic disperser, and then a membrane filter having a pore size of 0.2 μm is formed. To obtain a sample solution. 10 μL of this sample solution was injected into the apparatus together with the above-mentioned carrier solvent, detected using a refractive index detector (RI detector), and the molecular weight distribution of the measurement sample was measured using monodisperse polystyrene standard particles. Calculate using the line.
As standard polystyrene samples for the calibration curve measurement, molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , and 1 × 10 ⁴ , manufactured by Pressure Chemical Co., Ltd. Using at least 1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , at least about 10 standard polystyrene samples were measured, and a calibration curve was obtained. Create

<Fatty acid derivative>
The binder resin contained in the toner base particles according to the present invention preferably contains a fatty acid derivative in addition to the crystalline resin in view of the effect of lowering the viscosity of the binder resin.

  The fatty acid derivative according to the present invention is a compound obtained by reacting a fatty acid as a raw material with an alcohol, an amine, an alkaline earth metal or the like. Representative examples include fatty acid esters using fatty acids and alcohols as raw materials, fatty acid amide compounds using fatty acids and amines as raw materials, and metal soaps using fatty acids and alkaline earth metals as raw materials.

Among them, fatty acid alkylamide compounds are preferred. The following compounds are applied as the fatty acid alkylamide compound.
As the fatty acid alkylamide compound, a compound represented by R ₁ -CONR ₂ R ₃ is applied. In the formula, R ₁ is an aliphatic hydrocarbon group having 10 to 30 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
Here, the alkyl group, aryl group, and aralkyl group of R ₂ and R ₃ may be substituted with a usually inert substituent such as a fluorine atom, a chlorine atom, a cyano group, an alkoxy group, and an alkylthio group. However, preferably, at least one of R ₂ and R ₃ is a hydrogen atom, and more preferably an unsubstituted one. Fatty acid alkyl amide is contained as a crystallinity retaining component, and it is more preferable that, even in a low energy fixing (low temperature fixing) environment, the low temperature fixing property can be improved due to the effect of retaining the crystallinity of the crystalline polyester resin by the fatty acid amide compound. . Further, fixing offset and fixing wrapping can be prevented by the secondary effect of the fatty acid alkylamide compound. Further, when the terminal has a highly polar amide group, a strong interaction with the main resin is also exhibited, and the plastic effect of the main resin is promoted.

In the toner of the present invention, when the content of the crystalline resin is a [% by mass] and the content of the aliphatic derivative is b [% by mass], the value b / a of b to a is 0. It is preferably in the range of 1 to 1, more preferably in the range of 0.15 to 0.8.
The content of the crystalline resin and the aliphatic derivative controls the plasticization effect of the main resin and the promotion of plasticization of the crystalline resin. As described in the description of the fatty acid derivative (particularly, the fatty acid alkylamide compound), the fatty acid amide compound shows a strong interaction with the main resin and the crystalline resin through a highly polar amide bond. In other words, it is entangled with the main resin at a molecular level to further promote the molecular motion of the main resin, thereby lowering the Tg and bringing about a plasticizing effect. Also, it is considered that the plasticizing effect of the crystalline resin on the main resin can be enhanced by acting on the crystalline component in the same manner for the crystalline resin. Therefore, when b / a is 0.1 or more, the plasticizing effect of the fatty acid derivative can be brought out without excess crystalline resin, and the low-temperature fixability is excellent. Further, when b / a is 1 or less, the fatty acid derivative does not become excessive, and a decrease in the fixing and releasability of thin paper due to hot offset accompanying a decrease in viscosity can be suppressed.

  The melting point of the fatty acid derivative is preferably in the range of 40 to 110 ° C, more preferably in the range of 60 to 105 ° C. When the temperature is 40 ° C. or higher, the plasticizing effect of the main resin is promoted, while the fixing releasability caused by hot offset due to the lowering of viscosity is suppressed from being greatly reduced. On the other hand, the plasticizing effect (melting) can be promoted, and the effect of improving the fixing property can be exhibited.

  The fatty acid derivative preferably has a weight molecular weight in the range of 200 to 550, more preferably in the range of 250 to 500. When the weight molecular weight is 200 or more, while promoting the plasticizing effect of the main resin, it is possible to suppress a large decrease in fixing and peeling property due to hot offset due to a decrease in viscosity. The plasticizing effect (melting) can be promoted with respect to the applied heat, and the effect of improving the fixing property can be exhibited.

<Release agent>
The release agent is not particularly limited and various known ones can be used.For example, polyethylene wax, polyolefin wax such as polypropylene wax, branched hydrocarbon wax such as microcrystalline wax, Long chain hydrocarbon waxes such as paraffin wax and sasol wax, dialkyl ketone waxes such as distearyl ketone, carnauba wax, montan wax, behenyl behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentane Ester waxes such as erythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitate and distearyl maleate; Diamine behenyl amides, amide-based waxes such as trimellitic acid tristearyl amide.

  The content ratio of the release agent is preferably in the range of 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the release agent is within the above range, sufficient fixing and separating properties can be obtained.

  As a method of introducing the release agent into the toner particles, in the aggregation and fusing steps of the toner manufacturing method described below, fine particles consisting of the release agent alone are mixed together with the amorphous resin fine particles, the crystalline resin fine particles, and the like in an aqueous medium. For agglomeration and fusion. The release agent fine particles can be obtained as a dispersion in which the release agent is dispersed in an aqueous medium. The dispersion liquid of the release agent fine particles is prepared by heating an aqueous medium containing a surfactant to a temperature higher than the melting point of the release agent, adding the melted release agent solution, and adding mechanical energy such as mechanical stirring and ultrasonic energy. And finely dispersing the resulting mixture, followed by cooling.

  When the amorphous resin is, for example, styrene / acrylic resin, the release agent is previously compounded with the amorphous resin fine particles (styrene / acrylic resin fine particles) to be subjected to the aggregation and fusion steps. Thereby, the release agent can be introduced into the toner particles. Specifically, a release agent is dissolved in a solution of a polymerizable monomer for forming a styrene / acrylic resin, and this is added to an aqueous medium containing a surfactant, and mechanical stirring is performed in the same manner as described above. Amorphous containing a release agent by so-called mini-emulsion polymerization method, in which a fine dispersion is performed by applying a mechanical energy or ultrasonic energy or the like and then finely dispersing, and then adding a polymerization initiator and performing polymerization at a desired polymerization temperature. A dispersion of the conductive resin fine particles can be prepared.

<Colorant>
As the colorant, generally known dyes and pigments can be used.
As a colorant for obtaining a black toner, furnace black, carbon black such as channel black, magnetite, magnetic substances such as ferrite, dyes, various known inorganic materials such as inorganic pigments containing non-magnetic iron oxide can be used. Can be used. As a colorant for obtaining a color toner, a known colorant such as a dye or an organic pigment can be arbitrarily used.
Specifically, examples of the organic pigment include C.I. I. Pigment Red 5, 48: 1, 48: 2, 48: 3, 53: 1, 57: 1, 81: 4, 122, 139, 144, 149, 166, 177, 178, 222, 238, 269, C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Blue 15: 3, 60, and 76.

Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 68, 11, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 69, 70, 93, 95 and the like.
The colorant for obtaining the toner of each color can be used alone or in combination of two or more for each color.
The content ratio of the colorant is preferably in the range of 1 to 20 parts by mass, more preferably in the range of 4 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

<Components Constituting Toner Particles>
The toner base particles according to the present invention may contain an internal additive such as a charge control agent, if necessary, in addition to the binder resin, the colorant, and the release agent.

(Charge control agent)
Various known compounds can be used as the charge control agent.
The content ratio of the charge control agent is usually in the range of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the binder resin.

[Average particle size of toner particles]
The average particle size of the toner particles of the present invention is, for example, preferably in the range of 3 to 9 μm, more preferably in the range of 3 to 8 μm in terms of volume-based median diameter. The average particle size can be controlled by, for example, the concentration of the coagulant used, the amount of the organic solvent added, the fusing time, the composition of the polymer, etc. .
When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

  The volume-based median diameter of the toner particles is measured and calculated using a measuring device in which a computer system equipped with data processing software "Software V3.51" is connected to "Multisizer 3" (manufactured by Beckman Coulter). Things. Specifically, 0.02 g of the toner is added to 20 mL of the surfactant solution (for the purpose of dispersing the toner particles, for example, a neutral detergent containing a surfactant component is diluted 10 times with pure water). Then, ultrasonic dispersion was performed for 1 minute to prepare a toner dispersion, and this toner dispersion was placed in a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in a sample stand. Inject with a pipette until the indicated concentration of becomes 8%. Here, by setting the concentration within this range, a reproducible measured value can be obtained. Then, in the measuring device, the number of measured particles is set to 25,000, the aperture diameter is set to 50 μm, and the frequency value obtained by dividing the measurement range of 1 to 30 μm into 256 is calculated. % Is defined as a volume-based median diameter.

<Average circularity of toner particles>
From the viewpoint of improving transfer efficiency, the toner particles according to the present invention preferably have an average circularity of 0.930 to 1.000, more preferably 0.940 to 0.995. is there.
In the present invention, the average circularity of the toner particles is measured using “FPIA-3000” (manufactured by Sysmex).
More specifically, the sample (toner particles) was soaked in an aqueous solution containing a surfactant, subjected to ultrasonic dispersion treatment for 1 minute to disperse the sample, and then subjected to measurement conditions HPF using “FPIA-2100” (manufactured by Sysmex). In the (high-magnification imaging) mode, photographing is performed at an appropriate density of 3000 to 10000 HPFs detected, the circularity of each toner particle is calculated according to the following equation (T), and the circularity of each toner particle is added. , Is calculated by dividing by the total number of toner particles.
Equation (T): circularity = (perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)

<Softening point of toner>
The softening point of the toner is preferably in the range of 80 to 120C, more preferably in the range of 90 to 110C, from the viewpoint of obtaining low-temperature fixability of the toner.
The softening point of the toner is measured by a flow tester described below.
Specifically, first, under an environment of 20 ° C. and 50% RH, 1.1 g of a sample (toner) was placed in a petri dish, flattened, and allowed to stand for 12 hours or more. Then, a molding machine “SSP-10A” (Shimadzu) (Manufactured by Seisakusho Co., Ltd.) for 30 seconds with a force of 3820 kg / cm ² to produce a cylindrical molded sample having a diameter of 1 cm. Next, the molded sample was raised by a flow tester “CFT-500D” (manufactured by Shimadzu Corporation) at a load of 196 N (20 kgf), a starting temperature of 60 ° C., and a preheating time of 300 seconds in an environment of 24 ° C. and 50% RH. At a heating rate of 6 ° C./min, it is extruded from the end of preheating using a 1 cm diameter piston through a hole (1 mm diameter × 1 mm) of a cylindrical die, and an offset value of 5 mm is set by a melting temperature measuring method of a heating method. Is the softening point.

<External additives>
The toner particles according to the present invention can constitute the toner of the present invention as it is. However, in order to improve fluidity, chargeability, cleaning properties, and the like, the toner particles are provided with a so-called post-treatment agent, The toner of the present invention may be formed by adding an external additive such as a cleaning agent or a cleaning aid.

  As the post-treatment agent, for example, inorganic oxide fine particles such as silica fine particles, alumina fine particles, titanium oxide fine particles and the like, aluminum stearate fine particles, inorganic stearate compound fine particles such as zinc stearate fine particles, or strontium titanate, titanium Fine particles of an inorganic titanate compound such as zinc oxide are exemplified. These can be used alone or in combination of two or more.

It is preferable that these inorganic fine particles have been subjected to a surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil or the like in order to improve heat-resistant storage stability and environmental stability.
The total amount of these various external additives is in the range of 0.05 to 5 parts by mass, preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner. Various external additives may be used in combination.

[Method of Manufacturing Toner]
The method for producing a toner according to the present invention comprises the steps of: agglomerating and fusing fine particles of an amorphous vinyl resin to be formed into a binder resin and fine particles of a mixture of a crystalline resin and a fatty acid derivative dispersed in an aqueous medium. It is preferable to have a step of performing
Specifically, it is preferable to use an emulsion aggregation method in which fine particles in which an amorphous vinyl resin, a crystalline resin, and a fatty acid derivative are mixed are aggregated and fused to obtain toner particles.
In the emulsion aggregation method, a dispersion of fine particles of a resin constituting the binder resin and, if necessary, a dispersion of fine particles of other toner particle components are mixed with each other, and the repulsive force of the fine particle surface due to pH adjustment and the electrolyte are used. Agglomeration is slowly performed while maintaining the balance with the cohesive force due to the addition of the coagulant, and the association is performed while controlling the average particle size and the particle size distribution. Is carried out to produce toner particles.

As a specific example of a method for producing such a toner,
(1) A colorant particle dispersion preparing step of preparing a colorant particle dispersion by dispersing a colorant in an aqueous medium. (2) A crystalline resin and a fatty acid derivative are simultaneously emulsified and dispersed in an aqueous medium to prepare a crystalline resin. For preparing a crystalline resin particle dispersion liquid in which a fatty acid derivative is mixed with a crystalline resin particle dispersion liquid (3). A non-polymer containing a toner particle constituent such as a release agent and a charge control agent if necessary. Amorphous resin particle dispersion preparing step of dispersing an amorphous resin in an aqueous medium to prepare an amorphous resin particle dispersion (4) Amorphous resin particles, simultaneously mixed crystalline resin particles and colorant particles Aggregating and fusing step of forming agglomerated particles by aggregating and fusing in an aqueous medium (5) Aging step of aggregating the agglomerated particles by thermal energy to adjust the shape and preparing a toner particle dispersion liquid (6) Cooling to cool the toner particle dispersion Step (7): a filtration and washing step of solid-liquid separation of the toner particles from the cooled toner particle dispersion and removal of a surfactant and the like from the surface of the toner particles; and (8) a drying step of drying the washed toner particles. If necessary, (9) an external additive treatment step of adding an external additive to the dried toner particles can be added.

In the present invention, the “aqueous medium” refers to a medium comprising 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent.
Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran, and it is preferable to use an alcohol-based organic solvent that does not dissolve the obtained resin.

(1) Colorant Particle Dispersion Preparation Step A colorant particle dispersion can be prepared by dispersing a colorant in an aqueous medium. Since the colorant is uniformly dispersed, the colorant is preferably dispersed in an aqueous medium at a surfactant concentration of not less than the critical micelle concentration (CMC). Various known dispersers can be used as the disperser used for the colorant dispersion treatment.

(Surfactant)
Examples of the surfactant include anionic surfactants such as alkyl sulfates, polyoxyethylene (n) alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and phosphates, alkylamine salts, amino acids, and the like. Amine salt forms such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; and quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride Nonionic surfactants such as salt type cationic surfactants, fatty acid amide derivatives and polyhydric alcohol derivatives, alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N- Alkyl -N, N-amphoteric surfactants such as dimethyl ammonium betaine, and the like, also, the anionic surfactants and cationic surfactants having a fluoroalkyl group can be used.

The dispersion diameter of the colorant fine particles in the colorant particle dispersion prepared in this colorant particle dispersion preparation step is preferably in the range of 10 to 300 nm in terms of volume-based median diameter.
The volume-based median diameter of the colorant fine particles in the colorant particle dispersion is measured by an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”.
The coloring agent is introduced into the toner particles by dissolving or dispersing in a monomer solution for forming an amorphous resin in advance using a mini-emulsion method in an amorphous resin particle dispersion liquid preparing step described below. Is also good.

(2) Simultaneous Emulsion and Dispersion Preparation of Crystalline Resin and Fatty Acid Derivative Particle Mixed Liquid As a method of simultaneously emulsifying and dispersing the crystalline resin and the fatty acid derivative in an aqueous medium, the crystalline resin and the fatty acid derivative are dissolved or dissolved in an organic solvent. Disperse to prepare an oil phase liquid, prepare an aqueous medium (aqueous phase) containing a surfactant, and add an inorganic alkali compound or an organic alkali compound to the oil phase liquid or the aqueous phase, and then prepare the oil phase liquid. Is added to an aqueous phase, emulsified by mechanical shearing, for example, high-speed stirring, ultrasonic irradiation, etc. to form oil droplets, and then the organic solvent is removed.
Further, a so-called phase inversion emulsification method in which an aqueous phase is added to the above oil phase liquid can also be used.
The amount of the aqueous medium used is preferably in the range of 50 to 2,000 parts by mass with respect to 100 parts by mass of the oil phase liquid.
By setting the amount of the aqueous medium in the above range, the oil phase liquid can be emulsified and dispersed to a desired particle size in the aqueous medium.

Examples of the surfactant used include, for example, the same surfactants as described above.
As the organic solvent used for preparing the oil phase liquid, from the viewpoint of easy removal treatment after the formation of oil droplets, those having a low boiling point and low solubility in water are preferable, and specifically, Examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more.
The amount of the organic solvent used is usually in the range of 1 to 300 parts by mass, preferably 1 to 100 parts by mass, more preferably 25 to 70 parts by mass, based on 100 parts by mass of the crystalline resin and the fatty acid derivative.

The removal of the organic solvent after the formation of the oil droplets involves gradually increasing the temperature of the entire dispersion in which the toner particles are dispersed in the aqueous medium in a laminar stirring state, and providing strong stirring in a constant temperature range. After that, it can be performed by an operation such as desolvation.
The average particle diameter of the mixed resin fine particles obtained in the simultaneous dispersion liquid preparation step of the crystalline resin and the fine particles of the fatty acid derivative is preferably in the range of, for example, 50 to 500 nm as a volume-based median diameter.
The volume-based median diameter is measured using “UPA-150” (manufactured by Microtrac).

(3) Amorphous resin particle dispersion preparation step When the amorphous resin is a styrene / acrylic resin, the amorphous resin particle dispersion contains a surfactant having a concentration equal to or higher than the critical micelle formation concentration (CMC). To the aqueous medium, and add a polymerizable monomer for forming a styrene-acrylic resin to be an amorphous resin, and add a water-soluble polymerization initiator at a desired polymerization temperature while stirring to carry out polymerization. Thereby, an amorphous resin particle dispersion can be prepared.
On the other hand, similarly, when the amorphous resin is a styrene-acrylic resin, the amorphous resin particle dispersion is mixed with the amorphous resin in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. Add a monomer solution in which toner constituents such as a release agent and a charge control agent are dissolved or dispersed as necessary to the polymerizable monomer for forming the styrene / acrylic resin, In addition, a droplet is formed, and then a water-soluble radical polymerization initiator is added, and the polymerization reaction proceeds in the droplet to prepare an amorphous resin particle dispersion. Incidentally, an oil-soluble polymerization initiator may be contained in the droplet. In such an amorphous resin particle dispersion liquid preparation step, a forced emulsification (droplet formation) treatment by applying mechanical energy is essential. Examples of the means for applying mechanical energy include means for applying strong stirring or ultrasonic vibration energy, such as a homomixer, ultrasonic waves, and Manton-Gaulin.

The amorphous resin fine particles formed in the amorphous resin particle dispersion preparation step may have a structure of two or more layers composed of resins having different compositions. In this case, the emulsion polymerization treatment is performed according to a conventional method. It is possible to employ a method in which a polymerization initiator and a polymerizable monomer are added to the dispersion of the first resin particles prepared by (first-stage polymerization), and the system is subjected to a polymerization treatment (second-stage polymerization). it can.
When a surfactant is used in this step, for example, a surfactant similar to the above-described surfactant can be used.

(Polymerization initiator)
As the polymerization initiator to be used, various known polymerization initiators can be used. Specifically, for example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, -tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, bromomethylbenzoyl peroxide, Lauroyl oxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, formic acid-tert -Tert-butyl, tert-butyl peracetate, -tert-butyl perbenzoate, -tert-butyl perphenylacetate, -tert-butyl permethoxyacetate, and -tert-butyl perN- (3-toluyl) palmitate. Peroxides; 2 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis- (2-amidinopropane) nitrate, 1,1'-azobis (1-methylbutyronitrile-3-sulfonic acid sodium), 4 And azo compounds such as 4,4'-azobis-4-cyanovaleric acid and poly (tetraethylene glycol-2,2'-azobisisobutyrate). Among them, water-soluble polymerization initiators such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis- (2 -Amidinopropane) nitrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), and 4,4'-azobis-4-cyanovaleric acid can be preferably used. Further, as the polymerization initiator, a redox polymerization initiator such as persulfate and metabisulfite, and hydrogen peroxide and ascorbic acid can also be used.

(Chain transfer agent)
In the step of preparing the amorphous resin particle dispersion, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight of the amorphous resin. The chain transfer agent is not particularly limited, and examples thereof include an alkyl mercaptan and a mercapto fatty acid ester.
The average particle diameter of the amorphous resin fine particles obtained in the amorphous resin particle dispersion preparation step is preferably in the range of, for example, 50 to 500 nm as a volume-based median diameter. The volume-based median diameter is measured using “UPA-150” (manufactured by Microtrac).

(4) Aggregation and Fusing Step In this step, the colorant fine particles, the amorphous resin fine particles, and the simultaneously mixed resin fine particles of the crystalline resin and the fatty acid derivative formed in the above steps are aggregated and fused in an aqueous medium. Things. In this step, a non-crystalline resin particle dispersion, a simultaneously mixed resin particle dispersion of a crystalline resin and a fatty acid derivative, and a colorant particle dispersion are added to an aqueous medium, and these fine particles are aggregated and fused.
As a specific method of aggregating and fusing the colorant fine particles, the amorphous resin fine particles, and the simultaneously mixed resin fine particles of the crystalline resin and the fatty acid derivative, a coagulant is added to an aqueous medium so as to have a critical aggregation concentration or more. Then, by heating to a temperature equal to or higher than the glass transition point of the amorphous resin fine particles and higher than the melting peak temperature of the release agent and the crystalline resin, the colorant fine particles, the amorphous resin fine particles, and the crystal. Simultaneous mixing of a resin and a fatty acid derivative simultaneously promotes salting out of fine particles such as resin fine particles, and at the same time promotes fusion, and when the particles have grown to a desired particle diameter, adds a coagulation terminator to stop particle growth. In addition, this is a method in which heating is continued to control the particle shape as needed.

  In this method, it is preferable to heat the mixture to a temperature equal to or higher than the glass transition point of the amorphous resin fine particles related to the binder resin by shortening the time for which the coagulant is left after the addition, as short as possible. Although the reason for this is not clear, there is a problem that the aggregation state of the particles fluctuates depending on the standing time after salting out, the particle size distribution becomes unstable, and the surface properties of the fused particles fluctuate. This is because there is a concern that this will occur. The time up to the temperature rise is usually preferably within 30 minutes, more preferably within 10 minutes. Further, the heating rate is preferably 1 ° C./min or more. The upper limit of the heating rate is not particularly limited, but is preferably 15 ° C./min or less from the viewpoint of suppressing generation of coarse particles due to rapid fusion. Furthermore, after the reaction system reaches a temperature equal to or higher than the glass transition point, it is important to maintain the temperature of the reaction system for a certain period of time to continue the fusion. Thereby, the growth and fusion of the toner particles can be effectively advanced, and the durability of the finally obtained toner particles can be improved.

(Coagulant)
The flocculant to be used is not particularly limited, but one selected from metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum And the like. Specific metal salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate and the like. It is particularly preferable to use a divalent metal salt since the reaction can proceed. These can be used alone or in combination of two or more.
When a surfactant is used in this step, for example, a surfactant similar to the above-described surfactant can be used.

(5) Aging Step In this step, specifically, by heating and stirring the system containing the aggregated particles, the heating temperature, the stirring speed, and the heating time are controlled until the shape of the aggregated particles reaches a desired average circularity. And forming toner particles having a desired shape. In this step, it is preferable to control the shape of the toner particles by thermal energy (heating).

(6) Cooling Step to (8) Drying Step The cooling step, the filtration step, the washing step, and the drying step can be performed by employing various known methods.

(9) External Addition Processing Step The external addition processing step is a step of adding and mixing an external additive as necessary to the dried toner particles.
Examples of the method for adding the external additive include a dry method in which a powdery external additive is added to the dried toner particles and mixed. An apparatus can be used.
According to the above method for producing a toner, the toner of the present invention can be produced.

[Developer]
The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, or may be mixed with a carrier and used as a two-component developer.
As the carrier, for example, magnetic particles made of conventionally known materials such as iron, ferrite, and metals such as magnetite, alloys of these metals with metals such as aluminum, and lead can be used. It is preferable to use Further, as the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin-dispersed carrier obtained by dispersing a magnetic fine powder in a binder resin, or the like may be used.
The carrier preferably has a volume average particle size in the range of 15 to 100 μm, more preferably 25 to 80 μm.

[Image forming apparatus]
The toner of the present invention can be used in a general electrophotographic image forming method, and an image forming apparatus in which such an image forming method is performed includes, for example, a photosensitive member that is an electrostatic latent image carrier, Charging means for applying a uniform potential to the surface of the photoconductor by corona discharge having the same polarity as the toner; and electrostatic latent by performing image exposure on the surface of the uniformly charged photoconductor based on image data. Exposure means for forming an image, developing means for conveying toner to the surface of the photoreceptor to visualize the electrostatic latent image to form a toner image, and interposing the toner image via an intermediate transfer member as necessary And a fixing device for heating and fixing the toner image on the transfer material.
Further, the toner of the present invention can be suitably used at a relatively low temperature where the fixing temperature (surface temperature of the fixing member) is 100 to 200 ° C.

[Evaluation method of toner fixability]
The method for evaluating the fixability of the toner according to the present invention measures the dynamic viscoelastic strain dispersion under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%, and a stress-strain curve at a strain amplitude of 100%. And calculating the inclination of the major axis.
More specifically, as described in the above section <Method of calculating S130 and θ130> (measurement of dynamic viscoelastic strain dispersion) and (analysis of stress-strain curve), the dynamic viscoelastic strain dispersion measurement is used to calculate the stress. A distortion curve is created, and the integral value S130 of the stress of the curve and the inclination θ130 of the major axis are calculated to evaluate the minimum fixing temperature (fixing property) of the toner.
By using such an evaluation method, compared with the case where the effect on the fixing property is predicted from the softening point obtained by measuring the change in the melting state of the toner while applying a constant weight to the toner being heated. Thus, the fixing property of the toner can be more accurately predicted.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
[Preparation of Amorphous Vinyl Resin Particle Dispersion X1]
(1) First-stage polymerization 8 parts by mass of sodium dodecyl sulfate and 3000 parts by mass of ion-exchanged water were charged into a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, and stirred at 230 rpm under a nitrogen stream. While stirring at a high speed, the internal temperature of the reaction vessel was raised to 80 ° C. After the temperature was raised, an aqueous solution in which 10 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to the obtained mixture, and the temperature of the obtained mixture was again set to 80 ° C. After the monomer mixture 1 having the following composition was dropped into the mixture over 1 hour, the mixture was heated and stirred at 80 ° C. for 2 hours to carry out polymerization, whereby a dispersion a1 of resin fine particles was obtained. Prepared.
(Monomer mixture 1)
Styrene 480 parts by mass n-butyl acrylate 250 parts by mass Methacrylic acid 68 parts by mass

(2) Second-stage polymerization In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device, 7 parts by mass of sodium polyoxyethylene (2) dodecyl ether sulfate are dissolved in 3000 parts by mass of ion-exchanged water. The solution thus prepared was charged, the solution was heated to 80 ° C., and then a dispersion a1 (in terms of solid content) of 80 parts by mass of resin fine particles, a monomer having the following composition, and a release agent were dissolved at 90 ° C. Monomer mixture 2 and mixed and dispersed for 1 hour using a mechanical disperser “CLEARMIX” having a circulation path (manufactured by M Technic Co., Ltd., “CLEARMIX” is a registered trademark of the company) and emulsified particles. A dispersion containing (oil droplets) was prepared. The following behenyl behenate is a release agent, and its melting point is 73 ° C.
(Monomer mixture 2)
Styrene 285 parts by mass n-butyl acrylate 95 parts by mass Methacrylic acid 20 parts by mass n-octyl-3-mercaptopropionate 8 parts by mass Behenyl behenate 190 parts by mass Next, 6 parts by mass of potassium persulfate was ionized into the dispersion. An initiator solution dissolved in 200 parts by mass of exchanged water was added, and the resulting dispersion was heated and stirred at 84 ° C. for 1 hour to carry out polymerization to prepare a dispersion a2 of resin fine particles.

(3) Third-stage polymerization Further, 400 parts by mass of ion-exchanged water was added to the dispersion a2 of resin fine particles, and after sufficient mixing, 11 parts by mass of potassium persulfate was added to the dispersion obtained. A solution dissolved in parts by mass was added, and a monomer mixture 3 having the following composition was added dropwise at a temperature of 82 ° C. over 1 hour. After completion of the dropping, the dispersion was heated and stirred for 2 hours to carry out polymerization, and then cooled to 28 ° C. to prepare an amorphous vinyl resin particle dispersion X1 composed of a vinyl resin (styrene / acrylic resin). .
(Monomer mixture 3)
Styrene 307 parts by mass n-butyl acrylate 147 parts by mass methacrylic acid 52 parts by mass n-octyl-3-mercaptopropionate 8 parts by mass The physical properties of the obtained amorphous vinyl resin particle dispersion liquid X1 were measured. The volume-based median diameter (d ₅₀ ) of the conductive resin fine particles was 220 nm, the glass transition temperature (Tg) was 46 ° C., and the weight average molecular weight (Mw) was 32,000.

[Synthesis of crystalline polyester resin C1]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 0.4 mass parts of Ti (OBu) ₄ as a raw material monomer of the following polycondensation-based resin and an esterification catalyst were added. The reaction was carried out for 10 hours while distilling off water generated under a nitrogen stream.
450 parts by mass of sebacic acid 280 parts by mass of 1,6-hexanediol Thereafter, the temperature was raised to 210 ° C. at 10 ° C./hour, and the mixture was kept at 210 ° C. for 5 hours while distilling off water generated under a nitrogen gas stream. (8 kPa) for 1 hour to obtain a crystalline polyester resin C1. The obtained crystalline polyester resin C1 had a number average molecular weight (Mw) of 15000 and a melting point of 67 ° C.

[Fatty acid amide compound]
The following fatty acid amide compounds were used.
Fatty acid amide compound AS-1: melting point 100 ° C., Mw 283 (stearic acid amide)
Fatty acid amide compound AP-1: melting point 82 ° C., Mw 338 (erucamide)
Fatty acid amide compound AE-1: melting point 74 ° C., Mw 281 (oleic amide)
Fatty acid amide compound AL-1: melting point 35 ° C., Mw 531 (N-oleyl oleic amide)
Fatty acid amide compound AW-5: melting point 97 ° C., Mw 536 (N-stearyl stearamide)
Fatty acid amide compound AH-1: melting point 115 ° C., Mw 589 (ethylene bisoleic acid amide)

[Preparation of mixed aqueous dispersion ED-1]
30 parts by mass of the crystalline polyester resin C1 and 6 parts by mass of the fatty acid amide compound AS-1 were dissolved in methyl ethyl ketone and kept in a molten state. It was transferred at a transfer speed of 100 parts by mass per minute. Simultaneously with the transfer of the crystalline polyester resin C1 and the fatty acid amide compound AS-1 in the molten state, 84 parts by mass of the reagent ammonia water was diluted with ion-exchanged water in the aqueous solvent tank with respect to the emulsifying and dispersing machine. 0.37% by mass of dilute aqueous ammonia was transferred at a transfer rate of 0.1 liter per minute while heating to 100 ° C. with a heat exchanger. By operating this emulsifying and dispersing machine under the conditions of a rotation speed of a rotor of 60 Hz and a pressure of 5 kg / cm ² , the mixing of the crystalline polyester resin C1 having a volume-based median diameter of 220 nm and the fatty acid amide compound AS-1 was performed. An aqueous dispersion (simultaneous emulsification dispersion) ED-1 was prepared. The solids content was 23%.

[Preparation of mixed aqueous dispersions ED-2 to ED-6]
In the preparation of the mixed aqueous dispersion ED-1, the same procedure was repeated except that the fatty acid amide compound AS-1 was changed to AP-1, AE-1, AL-1, AW-5, and AH-1, respectively. A mixed aqueous dispersion (simultaneous emulsification dispersion) ED-2 to ED-6 of polyester resin fine C1 and each fatty acid amide compound was obtained.

[Preparation of amorphous polyester resin particle dispersion PA1]
(Synthesis of amorphous polyester resin X2)
Bisphenol A ethylene oxide 2.2 mol adduct 10 mol%
2.2 mol of bisphenol A propylene oxide adduct: 40 mol%
Terephthalic acid 22 mol%
15% fumaric acid
Dodecenyl succinic anhydride 11 mol%
Trimellitic anhydride 2 mol%
In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, the above-mentioned monomer components other than fumaric acid and trimellitic anhydride, and tin dioctanoate with respect to a total of 100 parts by mass of the above-mentioned monomer components 0.25 parts by mass was charged. After reacting at 235 ° C. for 6 hours in a nitrogen gas stream, the temperature was lowered to 200 ° C., and the above-mentioned fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerized under a pressure of 10 kPa until a desired molecular weight was obtained, to obtain a pale yellow transparent amorphous polyester resin (X2).
The obtained amorphous polyester resin (X2) has a glass transition temperature Tg of 59 ° C. by differential scanning calorimetry (DSC), a weight average molecular weight Mw of 23,000 by gel permeation chromatography GPC (standard substance: polystyrene), and a number The average molecular weight Mn was 7000, the softening temperature by a flow tester was 106 ° C., and the acid value measured according to JIS K0070-1966 was 11 mgKOH / g.

(Preparation of amorphous polyester resin particle dispersion liquid PA1)
A 3 liter reactor equipped with a jacket (BJ-30N, manufactured by Tokyo Rika Instruments Co., Ltd.) equipped with a condenser, a thermometer, a water dropping device and an anchor wing was maintained at 40 ° C. in a water circulating thermostat while the reactor was being cooled. A mixed solvent of 160 parts by mass of ethyl acetate and 100 parts by mass of isopropyl alcohol is added, and 300 parts by mass of the amorphous polyester resin (X2) is added thereto. The mixture is stirred at 150 rpm using a three-one motor and dissolved. Oil phase was obtained. To the stirred oil phase, 14 parts by mass of a 10% by mass aqueous ammonia solution was added dropwise for 5 minutes, and after mixing for 10 minutes, 900 parts by mass of ion-exchanged water was further added dropwise at a rate of 7 parts by minute. To give an emulsion.
Immediately, 800 parts by mass of the obtained emulsion and 700 parts by mass of ion-exchanged water were placed in a 2-liter eggplant flask, and set via a trap bulb in an evaporator (Tokyo Rikakikai Co., Ltd.) equipped with a vacuum control unit. . While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the pressure was reduced to 7 kPa while paying attention to bumping to remove the solvent. When the solvent recovery amount reached 1100 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. The resulting dispersion had no solvent odor. The volume-based median diameter (d ₅₀ ) of the resin particles in this dispersion was 130 nm as a value measured by a dynamic light scattering method using “Microtrack UPA-150” (manufactured by Nikkiso Co., Ltd.). . Thereafter, ion-exchanged water was added to adjust the solid content to 20% by mass, and this was used as an amorphous polyester resin dispersion (PA1).

[Preparation of Colorant Dispersion Cy1]
90 parts by mass of sodium dodecyl sulfate were added to 1600 parts by mass of ion-exchanged water. While stirring this solution, 420 parts by mass of copper phthalocyanine (CI Pigment Blue 15: 3) is gradually added, and then a dispersion treatment is performed using a stirrer “CLEARMIX” (manufactured by M Technic). Thus, an aqueous dispersion of colorant particles (colorant dispersion) (Cy1) was prepared.
With respect to the obtained aqueous dispersion (Cy1) of the colorant particles, the volume-based median diameter (d ₅₀ ) of the colorant particles was 110 nm.

[Preparation of release agent dispersion W1]
Behenyl behenate (ester wax, melting temperature 83 ° C) 270 parts by mass Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku) 13.5 parts by mass (active ingredient 60%, 3% based on mold release agent)
21.6 parts by mass of ion-exchanged water The above materials were mixed, and the release agent was dissolved at an inner liquid temperature of 120 ° C. with a pressure discharge type homogenizer (Gaulin homogenizer manufactured by Gorin), and then dispersed at a dispersion pressure of 5 MPa for 120 minutes. Subsequently, a dispersion treatment was performed at 40 MPa for 360 minutes, followed by cooling to obtain a dispersion. The solid content was adjusted to 20% by adding ion-exchanged water, and this was used as an aqueous dispersion (release agent dispersion) W1 of release agent particles. The volume average particle diameter of the particles in the release agent dispersion was 225 nm.

[Preparation of Toner 1]
Simultaneous emulsification and dispersion of the crystalline polyester resin C1 and the fatty acid amide compound AS-1 with 315 parts by mass (in terms of solid content) of the amorphous vinyl resin particle dispersion X1 in a reaction vessel equipped with a stirrer, a temperature sensor and a cooling pipe. 21.5 parts by mass of liquid ED-1 (in terms of solids), 1% by mass of sodium dodecyldiphenyletherdisulfonate (in terms of solids) in terms of resin ratio, and 2,000 parts by mass of ion-exchanged water were charged. At room temperature (25 ° C.), a 5 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 10. Further, 30 parts by mass (in terms of solid content) of the colorant particle dispersion liquid were charged, and a solution in which 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. . After standing for 3 minutes, the temperature was raised to 80 ° C. over 60 minutes, and after reaching 80 ° C., 21.5 parts by mass of a simultaneous emulsified dispersion ED-1 of the crystalline polyester resin C1 and the fatty acid amide compound AS-1 ( (In terms of solid content) and 90 parts by mass of ion-exchanged water.
The stirring speed was adjusted so that the growth rate of the particle diameter was 0.01 μm / min, and the particles were grown until the volume-based median diameter measured with a Coulter Multisizer 3 (manufactured by Beckman Coulter) reached 6.0 μm. Was.
Next, an aqueous solution in which 190 parts by mass of sodium chloride was dissolved in 760 parts by mass of ion-exchanged water was added to stop the growth of the particle diameter. Next, the mixture was heated and stirred at a temperature of 80 ° C., and the fusion of the toner base particles was advanced until the average circularity of the particles became 0.968, and the following washing and drying steps were performed.

<Washing / drying process>
The dispersion liquid of the toner base particles generated in the aggregation / fusion step was subjected to solid-liquid separation using a basket-type centrifuge to form a wet cake of the toner base particles. The wet cake was washed with ion-exchanged water at 35 ° C., and adjusted with a 25% aqueous sodium hydroxide solution until the pH reached 4.0 (corresponding to a Net strength of 0.10). The filtrate is washed with ion-exchanged water at 35 ° C. until the electric conductivity of the filtrate becomes 5 μS / cm in the basket type centrifuge, and then transferred to a “flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.)” to reduce the water content to 0. Drying was performed until the content became 5% by mass to prepare “toner base particles 1”.

<External additive treatment step>
1% by mass of hydrophobic silica (number-average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number-average primary particle size = 20 nm) were added to the “toner base particles 1”, and mixed with a Henschel mixer. Thus, a toner 1 was prepared.

[Preparation of Toner 2 to Toner 5]
Toners 2 to 5 were prepared in the same manner as in Toner 1 except that the pH of the toner 1 during washing with sodium hydroxide was changed as shown in Table I below.

[Production of Toners 6 to 20, 23 and 24]
In the preparation of Toner 1, Toners 6 to 20, 23 and 24 were prepared in the same manner as in Toner 1 except that the constitution of the toner was changed as shown in Table II below.

[Production of Toner 21]
Amorphous polyester resin particle dispersion PA1: 311.5 parts by mass (in terms of solid content)
Amorphous vinyl resin particle dispersion X1: 3.47 parts by mass (in terms of solid content)
Simultaneous emulsion dispersion ED-1 of crystalline polyester resin C1 and fatty acid amide compound AS-1: 21.5 parts by mass (solid content)
Colorant dispersion liquid Cy1: 30 parts by mass (solid content conversion)
Release agent dispersion W1: 25.6 parts by mass (solid content conversion)
Ion-exchanged water: 2000 parts by mass Anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Company): 6.5 parts by mass Put the above components in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer. At 25 ° C., 0.3M nitric acid was added to adjust the pH to 3.0, and then the prepared aluminum sulfate aqueous solution (SA) was dispersed while dispersing at 5000 rpm with a homogenizer (IKA Japan Ultratraax T50). 130 parts by mass were added and dispersed for 6 minutes.
Thereafter, a stirrer and a mantle heater are installed in the reaction vessel, and the rotation speed of the stirrer is adjusted so that the slurry is sufficiently stirred. After the temperature exceeded ℃, the temperature was increased at a rate of 0.05 ° C./min, and the particle size was measured every 10 minutes with a Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter). When the volume average particle size became 5.0 μm, the temperature was maintained, and 21.5 parts by mass (in terms of solid content) of the simultaneous emulsified dispersion ED-1 of the crystalline polyester resin C1 and the fatty acid amide compound AS-1 was added to 5 parts by mass. Charged over minutes. After being charged and kept for 30 minutes, the pH was adjusted to 9.0 with a 4% by mass aqueous sodium hydroxide solution. Thereafter, the temperature was raised to 90 ° C. at a rate of 1 ° C./min, and maintained at 90 ° C., while similarly adjusting the pH to 9.0 every 5 ° C. The fusion of the particles was advanced until the average circularity of the toner base particles became 0.968, and the container was cooled to 30 ° C. over 5 minutes with cooling water.
Note that the washing / drying step and the external additive treatment step were performed in the same manner as in the case of the toner 1, and a toner 21 was produced.

[Production of Toners 22 and 25]
Toners 21 and 25 were produced in the same manner as in the production of the toner 21 except that the constitution of the toner was changed as shown in Table II.

[Preparation of Developers 1 to 25]
100 parts by mass of a ferrite core and 5 parts by mass of a copolymer resin particle of cyclohexyl methacrylate / methyl methacrylate (copolymerization ratio: 5/5) are charged into a high-speed mixer equipped with stirring blades, and stirred and mixed at 120 ° C. for 30 minutes. A resin coat layer was formed on the surface of the ferrite core by the action of a mechanical impact force to obtain a carrier having a volume-based median diameter of 40 μm.
The volume-based median diameter of the carrier was measured by a laser diffraction particle size distribution analyzer “HELOS & RODOS” (manufactured by Sympathic) equipped with a wet disperser.
Toners 1 to 25 were added to each of the above carriers so that the toner concentration became 7% by mass, and the resulting mixture was charged into a micro-type V-type mixer (Tsutsui Rikagaku Kikai Co., Ltd.) and mixed at a rotation speed of 45 rpm for 30 minutes to form a developer 1 To 25 were prepared.

[Softening point of toner]
The softening point of the toner prepared above was measured by a flow tester shown below.
Specifically, first, in an environment of 20 ° C. and 50% RH, 1.1 g of each of the toners prepared above was put into a petri dish, flattened, and allowed to stand for 12 hours or more. Then, a molding machine “SSP-10A” ( (Shimadzu Corporation) with a pressure of 3820 kg / cm ² for 30 seconds to prepare a cylindrical molded sample having a diameter of 1 cm.
Next, the molded sample was raised by a flow tester “CFT-500D” (manufactured by Shimadzu Corporation) at a load of 196 N (20 kgf), a starting temperature of 60 ° C., and a preheating time of 300 seconds in an environment of 24 ° C. and 50% RH. At a heating rate of 6 ° C./min, it is extruded from the end of the preheating using a 1 cm diameter piston through a hole (1 mm diameter × 1 mm) of a cylindrical die, and an offset value of 5 mm is set by a melting temperature measuring method of a heating method. The offset method temperature Toffset measured in the above was taken as the softening point and is shown in Table III below.

[Calculation method of S130 and θ130]
For each of the toners produced above, S130 and θ130 were calculated by the following method.
(Dynamic viscoelastic strain dispersion measurement)
The measurement of distortion dispersion of the dynamic viscoelasticity of the toner was performed using ARES-G2 manufactured by TA Instruments. First, a pressure of 20 MPa was applied to 0.2 g of the toner powder by a compression molding machine for 30 seconds to produce pellets having a thickness of 2.0 mm ± 0.3 mm and 1 cmφ.
Next, the upper side of the pellet was set on an aluminum disposable parallel plate of 8 mmφ, and the lower side thereof was set on an aluminum disposable parallel plate of 25 mmφ. The melt was trimmed.
The sample was set so that the initial normal force was 0. Then, in the subsequent measurement, the effect of the normal force is canceled by setting the automatic tension adjustment (Auto Tension Adjustment ON). The measurement conditions were set as follows, and as shown in FIG. 4, three cycles of strain were applied for each strain amplitude, and the stress at that time was measured.
1. 1. Use a parallel plate with a diameter of 8 mm. 2. Set the measurement gap to 1 mm. 3. Set the frequency (Frequency) to 1 Hz. The applied strain amplitude (Strain) is 1.0% (Initial), 1.5%, 2.5%, 4%, 6%, 10%, 16%, 25%, 40%, 62%, 100%, Set to 158%, 250%, 400%, 500% (Final).

(Stress-strain curve analysis)
In the above-described dynamic viscoelastic strain dispersion measurement, stress data when a strain is applied for one cycle with a strain amplitude of 100% is collected, and the horizontal axis represents the strain γ, and the vertical axis represents the stress σ. A stress-strain curve is created such that the scale for 100% of the strain γ is equal to the scale for 1500 Pa of the stress σ. A stress-strain curve was similarly created for the remaining two cycles at a strain amplitude of 100%, and a stress-strain curve for a total of three cycles was obtained. FIG. 5 shows a stress-strain curve of the toner 1.
For each curve, the integrated value [Pa] of stress σ was calculated by TRIOS (manufactured by TA Instruments), and the integrated value of stress σ for three cycles of the curve was averaged to calculate S130 [Pa].
As shown in FIG. 3, a point A (a, b) having the longest distance from the center point (0, 0) of the stress-strain curve is specified, and the point A and the center point are connected by a straight line. Is assumed to be B at the point where the stress-strain curve intersects, and a straight line connecting point A and point B (passing through the center point) is defined as the major axis. The minor axis refers to a straight line that connects two points where a straight line that intersects the major axis at right angles and a stress-strain curve intersect. The inclination θ refers to the angle between the major axis and the horizontal axis, and can be calculated by obtaining tan θ = | b | / | a | from the coordinate value of the end point A (a, b) forming the major axis. Θ for three periods of the curve was averaged to obtain θ130 [°]. The obtained S130 and θ130 are shown in Table III below.

[Method of calculating θ70]
For each of the toners prepared above, θ70 was calculated by the following method.
The dynamic viscoelastic strain dispersion measurement was performed under the following condition A in the same manner as in the section of (Method for calculating S130 and θ130) (measurement of dynamic viscoelastic strain dispersion). In the following condition A, “strain amplitude: 1.0 to 500%” means that the applied strain amplitude is 1.0% (Initial), 1.5%, 2.5%, 4%, 6%, 10%. %, 16%, 25%, 40%, 62%, 100%, 158%, 250%, 400%, 500% (Final). As shown in FIG. 4, three cycles of strain were applied for each strain amplitude, and the stress at that time was measured.
<< Condition A >>
(1) Temperature: 130 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(2) Temperature: 100 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(3) Temperature: 70 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 100%
In the dynamic viscoelastic strain dispersion measurement under the condition A (3), data of stress when strain is applied for three cycles at a strain amplitude of 100% is collected, and the strain γ is plotted on the horizontal axis for each cycle. The stress σ is plotted on the vertical axis. At this time, a stress-strain curve is created so that the scale of 100% of the strain γ is equal to the scale of 250,000 Pa of the stress σ. Obtained. In this regard, θ70 [°] was calculated in the same manner as in the section (Stress-strain curve analysis) in <Calculation method of S130 and θ130>. The obtained θ70 is shown in Table III below.

[Evaluation]
<Under offset temperature (low temperature fixability)>
As an image forming apparatus, a commercially available full-color MFP “bizhub PRO (registered trademark) C1100” (manufactured by Konica Minolta Co., Ltd.) is used under the environment of normal temperature and normal humidity (temperature: 20 ° C., humidity: 50% RH). A roller modified so that the surface temperature of the fixing lower roller can be changed was used. A solid image with a toner adhesion amount of 8.0 g / m ² is output on a recording material “CF 80 g / m ² ” (manufactured by Mondi) at a fixing temperature of 460 mm / sec at a surface temperature of 120 to 170 ° C. This test was repeated until the cold offset occurred while changing the fixing temperature in steps of 2 ° C, and the lowest surface temperature of the upper fixing belt where the cold offset did not occur was investigated. The low-temperature fixability was evaluated as the temperature. In each test, the fixing temperature refers to the surface temperature of the upper fixing belt, and the surface temperature of the lower fixing roller was always set to a temperature lower by 20 ° C. than the upper fixing belt. The lower the minimum fixing temperature, the better the low-temperature fixability. In this evaluation, a case where the temperature was less than 144 ° C. was regarded as a pass.
(Evaluation criteria)
：: 132 ° C or less △: Higher than 132 ° C and less than 144 ° C ×: 144 ° C or more

<Media followability>
A4 size of npi quality 64.0g / ^{m 2} (manufactured by Nippon Paper Industries Co., Ltd.), (manufactured by Oji Paper Co., Ltd. Co., Ltd.) A4 size of POD gross coat 100g / ^{m 2,} and 8.5 inches × 11-inch HAMMERMILL TIDAL ( The evaluation was performed using INTERNATIONAL PAPER). The glossiness of each transfer material (white paper) on which no image is formed and the glossiness of a solid image are measured, and when the differences are defined as Δ (NPI), Δ (POD), and Δ (TIDAL), Δ (NPI ) -Δ (POD), Δ (NPI) −Δ (TIDAL), and Δ (POD) −Δ (TIDAL) with a maximum absolute value of 10 or less pose no practical problem. It was taken. It should be noted that the smaller the gloss difference, the better the media followability.
The gloss was measured using a gloss meter “micro-loss 75 °” (manufactured by BYK) at an incident angle of 75 ° with reference to an attached standard plate. The glossiness of the blank paper was the average value of five points at the center and four corners of the transfer material, and the glossiness of the solid image was the average value of five points at the center and four corners of the measured image.
As the image for evaluating the glossiness, a fixed solid image fixed at the lower fixing temperature + 20 ° C. in the under offset temperature evaluation was used.

<Fix separation property>
Using a modified machine of "bizhub (registered trademark) C754" (manufactured by Konica Minolta Co., Ltd.), the recording material "Kinto" was humidified by standing overnight in a normal temperature and normal humidity environment (25 ° C., 50% RH). 85g / m ² T ”(manufactured by Oji Paper Co., Ltd.) in a normal temperature and normal humidity environment (temperature 25 ° C., humidity 50% RH), a nip width 11.2 mm, a fixing time 34 msec, a fixing pressure 133 kPa, and an upper belt. At a fixing temperature of 130 ° C., a test in which a solid image with a toner adhesion amount of 4.0 g / m ² was output with a top margin of 8 mm was changed to reduce the top margin to 7 mm, 6 mm... In 1 mm units. The operation was repeated until a paper jam (jam) occurred, and the minimum leading edge margin in which no paper jam (jam) occurred was investigated, thereby evaluating the fixing / separating property. The smaller the minimum tip margin is, the better the fixing separation property is. In the present invention, a case where the level is “◎”, “○”, or “△” is regarded as a pass. (Evaluation criteria)
：: The top margin is 2 mm or less ○: The top margin is 3 mm or less Δ: The top margin is 4 mm or less ×: The top margin exceeds 4 mm.

From the above results, it is recognized that the toner of the present invention is superior to the toner of the comparative example in terms of low-temperature fixing property, medium followability, and fixing separation property.
In particular, when S130 is greater than 0 Pa and equal to or less than 100,000 Pa, it can be seen that the toner is superior in low-temperature fixability and media followability as compared with toner exceeding 100,000 Pa.
Also, when θ130 is in the range of 0 to 8 °, it is easy to expand due to deformation as compared with toner exceeding 8 °, so that it can be seen that the medium has excellent followability.
Further, the toner 2 having a net strength of sodium of 0.1 or more is superior in the fixing separation property as compared with the toner 4 having a net strength of less than 0.1, and the toner 2 has a net strength of 0.7 or less. Certain toner 3 is more excellent in media followability than toner 5 having a Net strength exceeding 0.7.

Claims (14)

An electrostatic latent image developing toner including toner particles containing a binder resin,
The binder resin contains an amorphous vinyl resin and a crystalline resin, and performs dynamic viscoelastic strain dispersion measurement under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%. When the integrated value of the stress of the stress-strain curve at an amplitude of 100% is S130, and the inclination of the major axis is θ130,
S130 is more than 0 Pa and not more than 350000 Pa,
The toner for developing an electrostatic latent image, wherein θ130 is 0 ° or more and less than 10 °.   2. The electrostatic latent image developing toner according to claim 1, wherein S130 is more than 0 Pa and 100000 Pa or less. 3.   The electrostatic latent image developing toner according to claim 1, wherein the θ130 is in a range of 0 to 8 °.   The electrostatic latent according to any one of claims 1 to 3, wherein a net intensity of sodium measured by X-ray fluorescence analysis is in a range of 0.1 to 0.7. Image developing toner.   5. The electrostatic device according to claim 1, wherein a content of the crystalline resin is in a range of 3 to 30% by mass based on a total amount of the binder resin. 6. Latent image developing toner.   The electrostatic latent image developing toner according to any one of claims 1 to 5, wherein the crystalline resin contains a crystalline polyester resin.   7. The electrostatic latent image developing toner according to claim 1, wherein the binder resin contains a fatty acid derivative in addition to the crystalline resin. 8.   When the content of the crystalline resin is a [mass%] and the content of the aliphatic derivative is b [mass%], the value b / a of b to a is in the range of 0.1 to 1. The toner for developing an electrostatic latent image according to claim 7, wherein:   9. The toner for developing an electrostatic latent image according to claim 7, wherein the fatty acid derivative is a fatty acid alkylamide compound.   The toner for developing an electrostatic latent image according to claim 9, wherein the fatty acid alkylamide compound has an amide bond at a molecular terminal.   The toner for developing an electrostatic latent image according to any one of claims 7 to 10, wherein the fatty acid derivative has a melting point in a range of 40 to 110 ° C.   The electrostatic latent image developing toner according to any one of claims 7 to 11, wherein the fatty acid derivative has a weight average molecular weight in a range of 200 to 550. The dynamic viscoelastic strain dispersion measurement is performed under the following various conditions A, and when the inclination of the major axis of the stress-strain curve at a strain amplitude of 100% under the following condition A (3) is θ70, the θ70 is 10 to 48 °. The toner for developing an electrostatic latent image according to claim 1, wherein the toner is in the range of:
<< Condition A >>
(1) Temperature: 130 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(2) Temperature: 100 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 500%
(3) Temperature: 70 ° C., frequency: 1 Hz, strain amplitude: 1.0 to 100%
Measure in order. A method for evaluating the fixability of a toner for developing an electrostatic latent image, comprising:
A dynamic viscoelastic strain dispersion measurement is performed under the conditions of a temperature of 130 ° C., a frequency of 1 Hz, and a strain amplitude of 1.0 to 500%, and an integrated value of a stress and a slope of a major axis of a stress-strain curve at a strain amplitude of 100% are calculated. A method for evaluating the fixability of the toner for developing an electrostatic latent image.

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